Anti-fouling compositions

ABSTRACT

An anti-fouling composition comprising a carrier, and a binder, the improvement which comprises an effective amount of at least one insecticide. The composition is applied to the surfaces of articles which come into contact with seawater or brackish water, especially wood. Other conventional anti-fouling agents may also be present.

This application has been filed under 35 USC 371 as the national stageof international application PCT/EP94/04087 filed Dec. 8, 1994.

The invention relates to a process and compositions for protectingagainst infestation of articles, especially ships' hulls, screens, nets,constructions, quays and signalling equipment, which come into contactwith seawater or brackish water.

Infestation by species of the group Lepadomorpha (goose barnacles), suchas various Lepas and Scalpellum species, or by species of the groupBalanomorpha (acom bamacles), such as Balanus or Pollicipes species,increases the frictional resistance of ships and leads as a result,through increased energy consumption and fent spells in dry dock, to amarked increase in the operating costs.

In addition to infestation by algae, for example Ectocarpus species andCerarium species, particular importance attaches to infestation bysessile Entomostraca groups, which are comprised under the nameCirripedia (curiped crustacens).

It is known, in addition, that insects can be controlled by means ofactive substances which act on the metamorphosis from the larval stageto the adult insect (K. H. Buichel, Pflanzenschutz undSchadlingsbekampftng [Plant protection and pest control], Georg ThiemeVerlag, Stuttgart 1977 Farm Chemicals Handbook, Meister Publ. Comp.1993; The Agrochemical Handbook, Third Edition, Royal Society ofChemistry, Cambridge 1991).

It has now been found that the insecticides, alone or in combinationwith other active substances, have an outstanding anti-fouling(anti-infestation) effect.

Since conventional anti-infestation compositions have a high content ofheavy metals, for example tin or copper, it is of advantage here that byusing the insecticides according to the invention it is now possible todispense with the use of heavy metal compounds such as, for example,bis(trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltinchloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulfide, antimony oxide, polymeric butyl titanate,phenyl-(bis-pyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, the zinc salt of 2-pyridinethiol 1-oxide,bisdimethyldithiocaibamoylzinc ethylenebisdithiocarbamate, zinc oxide,copper(I) ethylene-bis-dithiocarbanate, copper thiocyanate, coppernaphthenate and tributyltin halides, or substantially to reduce theconcentration of these compounds.

The application therefore relates to antifouling compositions comprisingat least one insecticide.

Preference is given to insecticides having a development-inhibitingaction which are capable of inhibiting the metamorphosis from crustaceanlarvae to the adult stage.

The insecticides which can be employed in accordance with the inventionare generally known and can come from different structural classes.

Particularly preferred compounds in the context of the invention arebenzoyl ureas such as triflumuron, chlorfluazuron, diflubermiron,flufenoxuron, flucycloxuron, hexaflumuron, penfluron, teflubenzron,nitroimines and nitromethylenes such as 1-[(6-chloro-3-pyridinyl)methyl]4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid), N-[(6-chloro-3-pyriyl)methyl-]N² -cyano-N¹-methylaceamides (NI-25);1-[4-(4chlorophenoxy)-3,5-dichlorophenyl]-3-(2,6-difluoro-benzoyl)-ureaandN-[[2,5-dichloro4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-amino]-carbonyl]-2,6-difluorobenzamide.

Preference is likewise given to development inhibitors from otherstructrral classes, for example benzoic acid[2-benzoyl-1(1,1-dimethylethyl)]-hydrazide,2,6-dimethoxy-N-[5-]4-(pentafluoroethoxy)phenyl[-1,3,4thiadiazol-2-yl]-bezamnide,N-cyclopropyl-1,3,5-triazine-2,4-triamine, 2-(4-phenoxyphenoxy)ethylethylcarbamate, 1-(decycloxy)-4[(6-methoxy4-hexinyl)-oxy]benzenes,(2-propinyl)4-methoxybenzoate, fenoxycarb, pyriproxyfen, triamathene,thiapronil, hexythiazox, clofentezine,4-chloro-5-(6-chloro-3-pyridyhnethoxy)2-3,4dichlorophenyl)pyridazin-3(2H)ones,buprofezin, hydroprene, kinoprene, methoprene, cycloprate, gush padan,paraxon, tribunil, isomers and triprene.

The active compounds mentioned here are given only by way of example;structurally related active substances having an insecticidal ordevelopment-inhibiting action are likewise suitable in principle foranti-fouling use. The following insecticides may be given as preferredexamples:

Phosphoric esters, such as azinphostyl, azinphos-methyl,-1(4-chlorophenyl)4-O-ethyl, S-propyl)phosphoryloxy-pymrl, chlorpyrifos,coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate,ethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophas,parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl,pirimiphos-methyl, profenofos, prothiofos, sulprofos, triazophos andtrichlorphon;

Carbamates, such as aldicarb, bendiocarb, -2-1-methylpropyl)phenylmethylcamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran,carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb,promecarb, propoxur and thiodicarb;

Organosilicon compounds,preferablydimethyl(phenyl)silyl-methyl3-phenoxybenzyl ethers, such as dimethyl-(4-ethoxyphenyl)-silylmethyl3-phenoxybenzyl ether, or [(dimethylphenyl)silyl-methyl2-phenoxy-6-pyridylmethyl etherssuchasforexampledimethyl(9-ethoxy-phenyl)-silylnethyl 2-phenoxy-pyridylmethylether, or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes, suchas, for example, (4-ethoxyphenyl)[3-(4fluoro-3-phenoxyphenyl-propyl]dimethyl-silane, sulafluofen;

Pyrethroids such as allethrin, alphamcthrin, bioresmetrin, byfenthrin,cycloprothrin, cyfluthtin, decanethrin, cyhalothrin, cypermerin,deltaamethrin,alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permetlrin, resmethrin and tralomethrin;

abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldeoxycarb,aldrin, amitraz, azamethiphos, bacillus thuringiensis, phosmet,phosphamidon, phosphine, prallethrin, propaphos, propetamphos,prothoate, pyraclofos, pyrethims, pyridaben, pyridafenthion, quinalphos,RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, sulfotep,sulfuryl fluoride, tar oils, tefluthrin, temephos, terbufos,tetrachlorovinphos, tetrametrin,O-2-tert.-butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, thiocyclam,thiofanox, thiometon, tralomethrin, triflumuron, trimethacarb,vamidothion, Verticillium, Lacanii, XMC, xylylcarb, benfiracarb,bensultap, bifenthrin, bioallethrin, MERbioallethrin, (S)-cyclopentenylisomer, bromophos, bromophosethyl, cadusafos, calcium polysulphide,carbophenothion, cartap, chinomethionate, chlordane, chlorfenvinphos,chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin,alphacypermethrin, cyophenothrin, cyromazine, dazomet, DDT,demeton-S-methylsulphon, diafenthiuron, dialifos, DEicrotophos, dinoseb,deoxabenzofos, diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN,esfenvalelrate, ethiofencarb, ethion, etofenprox, fenobucarb,fensulfothion, fipronil, flufenprox, fonofos, formetanate, formoothion,fosmethilan, furathocarb, heptachlor, IPSP, isazofos, isofenphos,isoprothiolane, isoxathion, iodifenphos, Kadethrin, lindane, malthion,mecarbam, mephosfolan, mercurous chloride, metam, Metarthizumanisopliae, methacrifos, methamidophos, methidathion, methiocarb,methoxychlor, methyl isothiocyanate, metholcarb, mevinphos,monocrotophos, naled, Neodidprion sertifer NPV, nicotine, omethoate,oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin,phenthoate, phorate.

Furthermore, synergistic effects are observed in the case ofcombinations of two or more of the insecticides mentioned. Thedevelopment inhibitors according to the invention are preferably alsoemployed in combination with algicides, herbicides, fungicides,molluscicides and/or other anti-fouling active substances, in which casesynergistic effects are likewise observed.

Co-cmponents which are employed with preference for the anti-foulingcompositions according to the invention are algicides such as diuron,dichlorophen, endothal, fentin acetate, quinoclamine, molluscicides suchas fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb andtrimethacarb, fungicides such as dichlofluanid, tolylfluanid,fluorfolpet, and azoles such as tebuconazole or customary anti-foulingactive substances such as2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,tetrabutyldistannoxane,2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,4,5-dichloro-2-noctyl4-isothiazolin-3-one,2,4,5,6tetrachloroisophthalonitrile, tetramethylthiuram disulfide,2,4,6-trichlorophenylmaleimide,2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine,diodrnethylparatrylsulfone, thiabendazol, tetrrphenylboron pyridinesalt, potassium salt, sodium salt and zinc salt of 2-pyridinethiol1-oxide.

The anti-fouling compositions according to the invention additionallycontain the customary constituents as described, for examnple, inUngerer, Chem. Ind. 37 (1985), 730-732 and Williams, Antifouling MarinCoatings 1973, Park Ridge: Noyes 1973.

Customary constituents in anti-fouling coating compositions are, inparticular, binders.

Examples of binders are polyvinyl chloride in a solvent system,chlorinated rubber in a solvent system, acrylic resins in a solventsystenm, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene rubbers,butadienejacrylonitrile rubbers, butadiene/styen/acrylonitrile rubbers,drying oils, such as linseed oil, asphalt and epoxy comnpounds, resinesters or modified hard resins in combination with tar or bitumen,chlorinated rubber, chlorinated polypropylene and vinyl resins.

The coating compositions may also contain inorganic pigments, organicpigments or dyes, which are preferably insoluble in seawater. Thecoating compositions may additionally contain materials such as rosinand/or rosin derivatives, in order to enable controlled release of thedevelopment inhibitors according to the invention. The coatings canadditionally contain plasticizers, modifying agents which influence therheological properties, and also other customary constituents. Thecompounds according to the invention or initially mentioned combinationscan also be incorporated in self-polishing anti-fouling systems.

Formulation examples, in which the active substances and/oractive-substance combinations described are preferably employed, aredescribed in DE 27 32 145 and EP 05 26 441.

Moreover, it has been found surprisingly that the mixtures of thedevelopment inhibitors according to the invention with algicides,herbicides and fungicides can also be used as wood preservatives. Thesemixtures are in this case effective in particular against insects,moulds, woodiscolouring fumgi and wood-destroying fimgi.

The following groups of microorganisms may be mentioned by way ofexample, but without representing any limitation:

A: Wood-discolouring fungi:

A1: Ascomycetes Ceratocystis such as Ceratocystis minor

A2: Deuteromycetes:

Aspergillus such as Aspergillus niger

Aureobasidium such as Aureobasidium pullulans

Dactylium such as Datylium fusarioides

Penicillium such as Penicillium brevicaule or

Penicillium variabile

Scierophorna such as Sclerophoma pithyophila

Scopularia such as Scopularia phycomyces

Trichoderma such as Trichoderma viride or

Trichoderma lignorum

A3: Zygomycetes Mucor such as Mucor spinorus

B: Wood-destroying fungi:

B1: Ascomycetes

Chaetomium such as Chaetomium globosum or

Chaetomium alba-arenulum

Humicola such as Humicola grisea

Petrella such as Petriella setifera

Trichurus such as Trichurus spiralis

B2: Basidiomycetes:

Coniophora such as Coniophora puteana

Coriolus such as Coriolus versicolor

Donkioporia such as Donkioporia expansa

Glenospora such as glenospora gaphii

Gloeophyllum such as Gloeophyllum abietinum or

Gloeophyllum adoratum or Gl. Protactum or

Gloeophyllum sepiarium or Gl. tabeum

Lentinus such as Lentinus cyathifonmes or

Lentinus edodes such as Lentinus lepideus or

Lentinus grinus or L. squarlosus

Paxillus such as Paxillus panuoides

Pleurotus such as Pleurotus ostr

Poria such as Poria monticola or Poria placenta

or Poria vaillantii or Poria vaporaria

Serpula such as Serpula hirantoides or Serpula lacryIans

Stereum such as Stereum hirsutum

Tyromyces such as Tyromyces palustris

B3: Deuteromycetes:

Alternaria such as Alternaria tenius

Cladosporium such as Cladosporium herbarumrn

C. Wood-destroying insects such as

C1: Beetles

Hylotupes bajulus, Chlorophorus pilosis, Anobium puncttm, Xestobiumrufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis,Priobium carpini, Lyctus brunneus, Lyctus aficanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.Dinoderus minutus

C2: Hymenoptera

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

C3: Termites

Kalotermes flavicollis, Cryptotermers brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes fonnosanus.

These wood preservatives generally contain from 0.01 to 50% by weight ofalgicides, herbicides and/or fingicides and from 0.00001 to 10% byweight of insecticides. Furthermore, the wood preservatives generallycontain more than 40% of a mixture of solvent and/or diluent and/ororganic-chemical binders or fixative, processing agent, dye, pigment,dye mixture or pigment mixture.

The mixtures contain as algicides for example:

copper sulphate, dichlororphen, endothal, fentin acetate, quinoclamine;

as herbicides for example:

acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim,ametryn, amidosulfiron, amitrole, ammonium sulfamate, anilofos, asulamatraine, aziptrotryne, benazlin, benfluralin, benfiresate, bensulfuron,bensulfide, bentazone, benzofencap, benzthiazuron, bifenox, bilanafos,borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron,difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor,dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb,dinoseb, dinoseb acetate, dinoseb, bromnacil, bromobutide, bromofenoxim,bromoxynil, butachlor, butamifos, fuenachlor, butralin, butylate,carbetamide, CGA 184927, chlorrethoxyfen, chloramben, chlorbromuron,chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen,chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron,chlorprepham, chlorsulfuron, chlorial, chlorthiarnid, cinmethylin,cinofulsuron, clethodini, clomazone, clomeprop, clopyralid, cyanamide,cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetiyn, diquat,dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine,endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate,fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M flazasulfuron,fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen,fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone,fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazonet,2,4-DB, desmedipharm, desmetryn, dicamba, dichlorbenil, isoproturon,isouron, isoxabe, isoxapyrifop, lactofen, lenacil, linuron, LS830556,MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefence, mefluidide,metam, metamiton, me or, me abiazuron, methazole, methoproptryne,methyldynron, methylisothiocyanate, metobromuron, fomosafen, fosamine,furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone,imazamethabenz, imazapyr, imazaquin, imzethapyr, ioxynil, isopropalin,propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, pyzazoxyfen,pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine,quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simaine,simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA,metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide,monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon,nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin,oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin,pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram,piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine,propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil,terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfliron,thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate,triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine,trifluralin, IBI-C4874 vemolate, propanil, propaquizafop, propazine,propham.

Preferred mixtures contain fungicides such as hexaconazole,tebuconazole, propiconazole, cycproconazoleand/or2-(1-chloro-cyclopropyl)l-2-chlorophenyl)3-1H-(1,2,4-triazol-1-yl)-propan-2-ol,preferably in a weight ratio with respect to the insecticide of from 1:9to 9:1.

Preferred additional fungicidal co-components are also:

bromuconazole, dichlobutazol, diniconazole, penconazole, methyl(E)methoximino-[a-(o-tolyloxy)o-tolyl)]acetate, methyl[E]-2-{2-[6-(2-cyanophenoxy)pyrimidin4yl-oxy]phenyl}-3-methoxyacrylate,meroxamn, carboxin, fenpiclonil,4(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pynrole-3-carbonitrile,butenafme and/or 3-iodo-2-propinyl n-butylcarbamate.

In addition it is possible to employ synergistically insecticidalco-components, such as the following insecticides:

phosphoric esters such as azinphos-ethyl, azinphos-methyl,α-1(4chlorophenyl)4(O-ethyl, S-propyl)phosphoryloxy-pyrazol,chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon,dichlorvos, dimethoate, ethoate. ethoprophos,

etrimfos, fenitrothion, fenthion, heptenophos, parathion,parthion-methl, phosalone, phoxim, pmphosethyl, pirimiphos-methyl,profenofosm prothiofos, sulfprofos, triazophos and trichlorphon;

Carbamates such as aldicarb, bendiocarb, a-2-(1-methylpropyl)-phenylmethylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofirn,carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb,promecarb, propoxur and thiodicarb;

organosilicon compounds, preferablydimethyl(phenyl)silyl-methyl-3-phenoxybenzyl ethers, such asdimethyl-(4-ethoxyphenyl)silylmethyl 3-phenoxybenzyl ether, or

(dimethylphenyl)silyl-methyl 2-phenoxy-6-pyridylmethyl ethers such asfor example dimethyl(9-ethoxy-phenyl)-silylmethyl2-phenoxy-6-pyridylmethyl ether, or[(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes, such as, forexample, (4-ethoxyphenyl)[3-(4-fluoro-3-phenoxyphenyl-propyl]dimethyl-silane, sila fluofin

Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfentnnn,cycloprotrin, cyfluthrin, decainethnn, cyhalothrin, cypermene n,deltaiettrin,alpha-yano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)cyclopropanecarboxylate,fenpropathrin, fenfluhrin, fenvalerate, flucythrinate, flumethri,fluvalinate, permethrin, resmethrin and tralometirin;

nitroimines and nitromethylenes, such as1-[(6-chloro-3-pyridinyl)methyl]4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid), N-[(6-chloro-3-pyridyl)methyl-]N² cyano-N¹-methylacetamide (NI-25),

abamectin, AC 303, 630, acephate, acrina alanycarb, aldoxycarb, aldrin,ammoniumbifluoride, amitraz, azamethiphos, bacillus thuringiensis,phosmet, phosphamidon, phosphine, prallethrin, propaphos, propetamphos,prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion,pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodiumhexafluorosilicate, sulfotep, sulfuryl fluoride, tar oils, teflubenzron,tefluthrin, temephos, terbufos, tetraclorovinphos, tenhriO-2-tert.-butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, thiocyclar,thiofanox, thiometon, tralomedirin, triflumuron, trimethacarb,vamidothion, Verticillium Lacanii, XMC, xylylcarb, benfuracarb,bensultap, bifentrin, bioallethrin, MERbioallethrin (S)-cyclopentenylisomer, bromophos, bromophos-ethyl, buprofezin, cadusafos, calciumpolysulphide, carbophenothion, cartap, chinomethionate, chlordane,chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin,chlorpyrifos, cyanophos, beta-cyflutirin, alpha-cypermethrin,cyophenothrin, cyromazine, dazomet, DDT, demeton-S-methylsulphone,diafenthiuron, dialifos, dicrotophos, diflubenzuron, dinoseb,dioxabenzofos, diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN,esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb,fensulfothion, fipronil, flucycloxuron, flufenprox, flufenoxuron,fonofos, formetanate, formothion, fosmethilan, furathiocarb, heptachlor,hexaflumuron, hydramtylnon, hydrogen cyanide, hydroprene, IPSP,isazofos, isofenphos, isoprothiolane, isoxathion, iodfenphos, Kadethrin,lindane, malathion, mecarbam, mephosfolan, mercurous, chloride, metam,Metarthizium, anisopliae, methacrifos, methamidophos, methidathion,methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb,mevinphos, monocrotophos, naled, Neodiprion sertifer NPV, nicotine,omethoate, oxydemetonmethyl, pentachlorophenol, petroleum oils,phenothrin, phenthoate, phorate;

Particularly preferred insecticides in this context are:

chlorpyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin,deltamethrin, permethrin, imidacloprid, hexaflumuron, lindane.

The synergistic effect of the mixtres is observed in mixing ratios offrom 99:1 to 1:99, preferably from 3:1 to 1:3, and with very particularpreference in a ratio of 1:1.

In order to obtain further increased actions against wood-destroyingfungi, it is also possible to admix the following fingicides, if desiredin addition to those mentioned above.

Triazoles:

amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole,fenbuconazole, fenchlorazole, fenetanil, fluquinconazole, flusilazole,flutriafol, imibenconazole, isazofos, myclobutanil, Opus, paclobuI,±)-cis-1-(4chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole,uniconazole;

imidazoles:

imazalil, pefurazoate, prochloraz,triflumizole,2-(1-tert.-butyl)1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,triazolcarboxanilides, such as2',6'-dibromo-2methyl-4-trifluoromethoxy4'-trifluoromethyl-1,3-triazole-5-caboxanilide.

copper salts:

copper sulfate, copper carbonate, copper chloride, copper-ammoniacomplexes, copperamnine complexes.

zinc salts:

zinc sulfate, zinc carbonate, zinc chloride.

mixed salts:

copper/boron mixtures, copper/chromiumbron mixtures,copper/chromium/arsenic mixtures.

Methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate,methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6(2,6-difluorophenoxy)pymidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3-(pyrimidin-2-yloxy]phenoxyl]phenyl]-3-methoxyacrylate,methyl(E)-2-[3-[5-(methylpyhmldin-2-yloxy]phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[3-[4-(nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate,methyl (E)-2-[2-phenoxyphenyl]-3-methoxyacrylate,methyl(E)-2-[2-3,5-dimethylbezyl)pyrrol-1-yl]-3-methoxyacrylate, methyl(E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-2-(2-(phenylethen-1-yl)phenyl]-3-methoxyacrylatemethyl(E)-2-[2-3,5-chlorophenoxy)-pyridin-3-yl]3-methoxyacrylate,methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)-phenyl)-3-methoxyacrylate,methyl (E)-2-(2-[3-(alpha-hydroxbenzy)phenoxy)phenyl)-3-methoxyacrylate,methyl (E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate,methyl (E)-2-[2-3-n-propyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylatemethyl(E)-2-[2-[3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(3-ethoxyphenoxy)phenyl]-3-methoxyacrylatemethyl(E)-2-[2-(4-tert.butylpyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylatemethyl(E)-2-[243-methylpyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2-methylphenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)2-[2-5-bromopyridin-2-yloxymethyl]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxylphenoxy)-phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6(2-chloropyridin-3-yloxy]pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,(E),(E)methyl-2-[2-(5,6dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methoxyacrylate,(E)methyl-2-{2-[6-[6-methylpyridin-2-yloxy)pyrimidin-4yloxy)phenyl}-3-methoxyacrylate,(E),(E) methyl-2-{2-(3-methoxyphenyl)methyloximinomethyl)phenyl}-3-methoxyacrylate,(E)methyl-2-{2-(6-(2-azidophenoxy)pyrimidin-4-yloxylphenyl}3-methoxyacrylate,(E),(E) methyl-2-{2-[6-phenylpyrimidin4-yl)methyloximinomethyl)phenyl}-3-methoxyacrylate, (E),(E)methyl-2-{2-[(4-cglorophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate,(E)methyl-2-{2-[6-(2-n-propylphenoxy)1,3,5-triazinfyloxy]phenyl}-3-methoxyacrylate,(E),(E)methyl -2-{2-[(3-nitrophenyl)methyloximinomethyl)phenyl}-3-methoxyacrylate.

Succinate dehydrogenase inhibitors such as:

fenfurar, flrcarbanil, cyclafluramide, furmecyclox, Seedvax,metsulfovax, pyrocarbolide, oxycarboxin, Shirlan, mebenil (mepronil),benodanil, flutolanil (Moncut)

naphthalene derivatives such as:

terbinafine, naftifine, butenafine,3-chloro-7-2-aza-2,7,7-trimethyl-oct-3-en-5-ine)

sulfenamides such as dichlorofluanid, tolylfluanid, folpet, fluorfolpet;captan, captofol,

benzimidazoles, such as carbendazirn, benomyl, firathiocarb,fuberidazole, thiophonatmethyl, thiabendazole or salts thereof;

thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate; quaternary ammonium compounds such asbenzyldimethyltetradecylarmmonium chloride,benzyldimethyldodecyclammonium chloride, didecyldimethylammoniumchloride,

morpholine derivatives such as tridemorph, fenpropimorph, falinorph,dimethomorph, dodemorph; aldimorph, fenpropidin and arylsulfonic saltsthereof, for example p-toluenesulfonic acid and p-dodecylphenyl-sulfonicacid,

iodine derivatives such as diiodomethyl p-tolyl sulfone,3-iodo-2-propinyl alcohol, 4 chlorophenyl 3-iodopropargyl fonnal,3-bromo-2,3-diiodo-2-propenyl ethylcarbate, 2,3,3-triiodallylalcohol,3-bromo-2,3-diiodo-2-propenyl alcohol, 6iodo-3-oxo-hex-5-inolbutylcarbamate,6iodo-3-oxo-hex-5-in-ol-phenylcarbamate,3-iod-2-propinyl-n-hexylcarbamate,3-iod-2-propinyl-cyclohexylcarbamate,3-iodo-2-propinyl phenylcarbamate;

phenol derivatives such as tribromophenol, tetrachlorophenol,3-methylfhlorophenyl, dichlorophen, o-phenylphenol, m-phenylphenol,p-phenylphenol, 2-benzyl-4-chlorophenol;

glutaraldehyde; bromine derivatives such as2-bromo-2-nitro-1,3-propanediol;

isothiazolinones, such as N-methylisothiazolin-3-one,5-chloro-N-methyl-isothiazoline-3-one,4,5-dichloro-N-octyliso-thiazolin-3-one, Ntyl-isothiazolin-3-one;

benzisothiazolinones, 4,5-trimethylene-isothiazolinones;

pyridines or pyrimidines, such as 1-hydroxy-2-pyridinethione (and theirNa, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine,pyrimethanil, mepanipyrim, dipyrithion;

metal soaps, such as tin naphthenate, copper naphthenate, zincnaphthenate, tin octoate, copper octoate, zinc octoate, tin2-eylhexanoate, copper 2-ethylhexanoate, zinc 2-ethylhexanoate, oleate,tin phosphate, copper phosphate, zinc phosphate, tin beneoate, copperbenzoate and zinc benzoate;

oxides such as tributyltin oxide, Cu₂ 2O, CuO, ZnO;

dialkyldithiocarbamates, such as Na salts and Zn salts ofdialkyldithiocarbamates, tetramethylthiuram disulfide;

dithiocarbamates, cuiraneb, ferbam, mancopper, mancozeb, maneb, metam,metirm, thiram zineb, ziram:

nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile,2,3,5,6-tetrafluoroterephthalodinitrile;

benzthiazoles such as 2-mercaptobenzothiazole; quinolines, such as8-hydroxyquinoline and Cu salts thereof;

benzamides, such as 2,6dichloro-N(4-trifluoromethylbenzyl)benzamide(XRD-563);

boron compounds, such as boric acid, boric esters, borax;

formaldehyde and formaldehyde-donor compounds, such as benzyl alcoholmono(poly)-hemiformal, oxazolidine, hexa-hydro-S-triazine,N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid,tecloftalam;

tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclo-hexyldiazeniumdioxy)tributyltinand K salts, bis-N-cyclohexyldiazeniumdioxy)-copper.

Furthermore, highly active compounds are also produced with thefollowing active substances:

fungicides acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl,bupirint, chinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet,diclomezine, dichloram, diethofencarb, dimethirimol, dinocab, dithianon,dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol,fenitropan, fentin acetate, fentin hydroxide, ferimzone, fluazinam,fluromide, flusulfamide, flutriafol, fosetyl, fthalide, furalaxyl,guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl,methasulfocarb, nitrothalisopropyl, nuarimol, oflurace, oxadiyl,perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin,procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon,quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl,tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine,vinclozolin.

The weight ratios of the active substances in these active-substancecombinations can be varied within relatively large ranges.

The active-substance combinations preferably obtain the insecticidalactive substance in a proportion of from 0.1 to 99.9%, in particularfrom 1 to 75%, particularly preferably from 5 to 50%, the remainder to100% being made up by one or more of the above-mentioned co-components.

The quantity of the compositions and/or concentrates employed isdependent on the nature and incidence of the insects, microorganisms, onthe germ count and on the medium. The optimum quantity for use in theapplication can be determined in each case by a series of tests. Ingeneral, however, it is sufficient to employ from 0.001 to 20% byweight, preferably from 0.05 to 10% by weight, of the active-substancemixture, relative to the material to be protected.

The active-substance mixture can be used as such, in the form ofconcentrates or generally customary formulations, such as solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a mnner known per se, forexample by mixing the active substances with solvents and/or diluents,emulsifier, dis sant and/or binder or fixative, water repellent, ifdesired siccatives and UV stabilizers, and, if desired, dyes andpigments, and also firther processing auxiliaries.

The solvent and/or diluent is an organic-chemical solvent or solventmixtu and/or an oily or oil-like, relatively non-volatileorganic-chemical solvent or solvent mixture and/or a polarorganic-chemical solvent or solvent mixture and/or water and at leastone emulsifier and/or wetting agent or consists thereof

As organic-chemical solvents it is preferred to employ oil or oil-likesolvents having an evaporation number of more han 35 and a flash pointof more than 30° C., preferably more than 45° C. As such relativelynon-volatile, water-insoluble, oily and oil-like solvents, use is madeof appropriate mineral oils or their aromatic fractions or mineraloil-containing solvent mixtures, preferably white spirit, petroleumand/or alkylbe ee.

Those employed with advantage are mineral oils having a boiling range offrom 170 to 220° C., white spirit having a boiling range of from 170 to220° C., spindle oil having a boiling range of from 250 to 350° C.,petroleum or aromatics with a boiling range from 160 to 280° C.,turpentine oil and the like.

In a preferred embodiment, use is made of liquid aliphatic hydrocarbonshaving a boiling range of from 180 to 210° C. or high-boiling mixturesof aromatic and aliphatic hydrocarbons having a boiling range of from180 to 220° C. and/or spindle oil and/or monochloronaphthalene,preferably α-mmonochloronaphtalene.

The organic, relatively non-volatile oily or oil-like solvents having anevaporation number of more than 35 and a flash point of above 30° C.,preferably of above 45° C., can be replaced in part by readily ormoderately volatile organic-chemical solvents, with the proviso that thesolvent mixture likewise has an evaporation number of more than 35 and aflash point of more than 30° C., preferably more than 45° C., and thatthe insecticideifungicide mixture is soluble or emulsifiable in thissolvent mixture.

In accordance with a preferred embodiment, part of the organic-chemicalsolvent or solvent mixture is replaced or an aliphatic polarorganicchemical solvent or solvent mixture. Preferably, aliphaticorganic-chemical solvents containing hydroxyl and/or ester and/or ethergroups are used, for example glycol ethers, esters or the like.

As a solvent or diluent, water in particular is also suitable, which maybe mixed with one or more of the abovementioned organic-chemicalsolvents or diluents, emulsifiers and dispersants.

The organic-chemical binders which are used in the context of thepresent invention are the synthetic resins which are known per se andwhich are water-ilutable and/or dispersible or emulsifiable or solublein the organic-chemical solvents employed, and/or binding drying oils,especially binders consisting of or comprising an acrylic resin, a vinylresin, for example polyvinyl acetate, polyester resin, condensationpolymer resin or addition polymer resin, polyurethane resin, alkyd resinor modified alkyd resin, phenolic resin, hydrocarbon resin, such asindene-coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

The synthetic resin used as binder can be employed in the form ofemulsion, dispersion or solution. As binders it is also possible to usebitumen or bituminous substances in a proportion of up to 10% by weight.In addition, dyes, pigments, water repellents, odour correctors andinhibitors and/or anticorrosion agents and the like which are known perse can be employed.

According to the invention, it is preferred as organic-chemical binderfor at least one alkyd resin or modified alkyd resin and/or a dryingvegetable oil to be present in the composition or in the concentrate. Itis preferred according to the invention to use alkyd resins having anoil content of more than 45% by weight, preferably from 50 to 68% byweight.

The binder mentioned can be replaced wholly or partially by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active substances and crystallization orprecipitation. They preferably replace from 0.01 to 30% of the binder(based on 100% of the binder employed).

The plasticizers derived from the chemical classes of the phthalicesters, such as dibutyl phthalate, dioctyl phthalate or beneyl butylphthalate, phosphoric esters, such as tributyl phosphate, adipic esters,such as di(2-ylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or relativelyhigh molecular weight glycol ethers, glycerol esters andptoluenesulfonic esters.

The chemical basis of fixatives, for example, is polyvinyl alkyl ethers,such as polyvinyl methyl ether, or ketones, such as benzophenone andethylenebenzophenone, or nitrogen compounds such as alklolanines andanmonia.

The wood which can be protected by the active-substance m according tothe invention or by compositions containing the latter is to beunderstood, for example, as: constructional timber, wooden beams,railway sleepers, bridge components, jetties, wooden vehicles, crates,pallets, containers, telephone poles, wooden panelling, wooden windowsand doors, plywood, chipboard, joinery work or wooden products which areused quite generally in house building or in joinery.

Particularly effective wood protection is obtained by large-scaleindustrial impregnation processes, for example vacuurn, double vacuun orpressure processes.

The microbicidal compositions or concentrates used for protecting woodand wooden materials contain the active-substance combination in aconcentration of from 0.01 to 95% by weight, in particular from 0.01 to60% by weight.

Preferred compositions (ready-to-use compositions) preferably containfrom 0.2 to 3% by weight, in particular from 0.5 to 2% by weight, of amixture of Alsystin with fungicides, herbicides and/or algicides and atleast one organic-chemical solvent or solvent mixture and/or an oily oroil-like relatively non-volatile organic-chemical solvent or solventmixture and/or a polar organic-chemical solvent or solvent mixre and/orwater and emulsifier and/or wetting agent and, if desired, from 0 to 5%by weight, preferably fiom 0.1 to 3% by weight, of fixative and/or otheradditional agents as the residual constituent.

Particularly preferred (ready-to-use) compositions contain 2 to 30% byweight, preferably from 5 to 22% by weight, calculated as solids, of asynthetic-resin binder, preferably an alkyd resin and/or a dryingvegetable oil, and at least one organic-chemical solvent or solventmixture and/or an oily or oil-like relatively non-volatileorganic-chemical solvent or solvent mixture and/or a polarorganic-chemical solvent or solvent mixture and/or water and emulsifierand/or wetting agent and, if desired, siccatives, dyes, colour pigments,anti-settling agents and/or UV stabilizers as the residual constituent.

Concentrates for preserving wood and wooden materials preferably containfrom 0.2 to 25% by weight, preferably from 3 to 8% by weight, of arnixtr of Alsystin with fungicides, herbicides or algicides, from 5 to40% by weight, preferably from 10 to 30% by weight (calculated assolids), of at least one organic-chemical binder and/or fixative orplasticizer and, in addition, an organic-chemical solvent or solventmixture and/or an oily or oil-like relatively non-volatileorganic-chemical solvent or solvent mixture and/or a polarorganic-chemical solvent or solvent mixture and/or a penetrationauxiliary and/or water and an emulsifier and/or wetting agent as theresidual constituent.

The compositions according to the invention make it possible in anadvantageous manner to replace the microbicidal compositions availableat present by more effective compositions. They exhibit good stabilityand, advantageously, have a broad spectrum of action.

EXAMPLE 1

Instead of the direct testing of balanides, Arternia salina was used insearching for substances having a development-inhibiting effect onCrustaceae.

This saltwater crustacean is highly suitable because of its many larvalstages and the established test systems, which are recognizedinternationally. Because of the different sensitivities of the naupliusstages, synchronized populations were used for testing (R. B. Sleet andK. Brendel: Homogeneous populations of Artemia nauplii and theirpotential etc for in vitro testing in developmental toxicology,Teratogenesis, Carcinogenesis and Mtagenesis 5; 41-54 (1985)). The testswere carried out in accordance with the procedure published by Sorgeloosand co-workers (P. Sorgeloos, C. R van der Wielen and G. Persoone: Theuse of Artemia nauplii for toxicity tests--a critical analysis,Ecotoxicology and Environmental Sefety 2, 249-255 (1978)).

Rating: 3=100% mortality

2=50%, <100% mortality

1=20-50% mortality

0=no action

                  TABLE 1                                                         ______________________________________                                        Result for some compounds according to the invention                                       μg of active substance                                        Active substance                                                                           per ml of incubation medium                                                                    Rating                                          ______________________________________                                        Alsystin     10               3                                               Chlorofluazuron                                                                            10               3                                               Methoprene   100              3                                                            10               1-2                                             Hydroprene   100              3                                               Pyriproxylen 100              3                                                            10               3                                               ______________________________________                                    

We claim:
 1. An anti-fouling composition comprising:a) an anti-foulingeffective amount of at least one insecticide selected from the groupconsisting of;i) triflumuron; ii) chlorfluazuron; iii) diflubenzuron;iv) flufenoxuron; v) flucycloxuron; vi) hexaflumuron; vii) penfluron;viii) teflubenzuron; ix) 1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imdazol-2-amine (imidacloprid); x)N-[(6chloro-3-pyridinyl)-methyl]-N² -cyano-N¹ -methylacetarnide (NI-25);xi)1-[4-(4chlorophenoxy),3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)-urea;and xii)N-[[[2,5dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-amino]-carbonyl]-2,6-difluorobenzamide;b) a carrier; and c) a binder selected from the group consisting ofi)solvent systems comprising polyvinyl chloride; ii) solvent systemscomprising chlorinated rubber; iii) aqueous dispersions comprising vinylchloride/vinyl acetate copolymers; iv) organic solvent systemscomprising vinyl chloride/vinyl acetate copolymers; v) butadiene/styrenerubbers; vi) butadiene/acrylonitrile rubbers; vii)butadiene/styrene/acrylonitrile rubbers; viii) drying oils; ix) asphalt;x) epoxy compounds; xi) resin esters or modified hard resins incombination with tar or bitumen; xii) chlorinated rubber; xiii)chlorinated polypropylene; and xiv) vinyl resins.
 2. An anti-foulingcomposition according to claim 1, additionally comprising at least onealgicide, herbicide, fungicide, molluscicide or other compoundexhibiting anti-fouling activity.
 3. An anti-fouling compositionaccording to claim 1, wherein the insecticide is selected from the groupconsisting of triflumuron and chlorfluazuron, and the anti-foulingcomposition further comprises at least one algicide, herbicide,fungicide, molluscicide or other compound exhibiting anti-foulingactivity.
 4. A method of protecting articles which come into contactwith seawater and brackish water, said method comprising applying tosuch articles an anti-fouling effective amount of an anti-foulingcomposition comprising:a) an anti-fouling effective amount of at leastone insecticide selected from the group consisting of:i) triflumuron;ii) chlorfluazuron; iii) diflubenzuron; iv) flufenoxuron; v)flucycloxuron; vi) hexaflumuron; vii) penfluron; viii) teflubenzuron;ix)1-[(6-chloro-3-pyridinyl)-methyl]4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid); x) N-[(6-chloro-3-pyridinyl)-methyl]-N² -cyano-N¹-methylacetamide (NI-25); xi)1-[4-(4-chlorophenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)-urea;and xii)N-[[[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-amino]-carbonyl]-2,6-difluorobenzamide;b) a carrier; and c) a binder.
 5. The method according to claim 4,wherein a surface of the article to be protected comprises wood.
 6. Themethod according to claim 4, wherein said anti-fouling compositionfurther comprises at least one algicide, herbicide, fungicide,molluscicide or other compound exhibiting anti-fouling activity.
 7. Themethod according to claim 4, wherein the insecticide is selected fromthe group consisting of triflumuron and chlorofluazuron, and theanti-fouling composition further comprises at least one algicide,herbicide, fungicide, molluscicide or other compound exhibitinganti-fouling activity.